WO2013034158A1 - Composition de peinture antisalissure auto-polissante comprenant des particules solides de constituant de colophane piégés ou encapsulés - Google Patents

Composition de peinture antisalissure auto-polissante comprenant des particules solides de constituant de colophane piégés ou encapsulés Download PDF

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Publication number
WO2013034158A1
WO2013034158A1 PCT/DK2012/050331 DK2012050331W WO2013034158A1 WO 2013034158 A1 WO2013034158 A1 WO 2013034158A1 DK 2012050331 W DK2012050331 W DK 2012050331W WO 2013034158 A1 WO2013034158 A1 WO 2013034158A1
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WO
WIPO (PCT)
Prior art keywords
rosin
paint composition
constituents
solid particles
paint
Prior art date
Application number
PCT/DK2012/050331
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English (en)
Inventor
Stefan Møller OLSEN
Diego Meseguer YEBRA
Torben Schandel
Original Assignee
Hempel A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hempel A/S filed Critical Hempel A/S
Priority to CN201280043063.4A priority Critical patent/CN103857754A/zh
Priority to EP12829513.6A priority patent/EP2753665A4/fr
Priority to US14/342,948 priority patent/US20140242403A1/en
Publication of WO2013034158A1 publication Critical patent/WO2013034158A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31844—Of natural gum, rosin, natural oil or lac

Definitions

  • the present invention relates to seif-poiishing antifouiing paint composition
  • a seif-poiishing antifouiing paint composition comprising solid particles of entrapped or encapsulated rosin constituents. Solid particles of this nature render it possible to substitute a portion of seawater-solu ble pigments such as Cu 2 0 and ZnO.
  • the surface area of the pore walls of the leached layer determines the extent of the degradation/dissolution of the binder.
  • the binder at the paint surface has been degraded/dissolved to a given extent (after the so-called "lag-time"), the surface becomes weak enough to be dissolved/eroded by the action of moving seawater.
  • seawater soluble pigments such as Cu 2 0 and/or ZnO are replaced by less soluble particles, the leached layer's pore wall surface area is diminished, and so is the rate of degradation/dissolution of the binder. This typically leads to a lower polishing rate and increased leached layer thickness.
  • thicker leach layers lead to increased diffusion resistance of the active ingredients in the coating, leading to lower flux at the seawater-coating interphase and, ultimately, to reduced antifouiing performance.
  • seawater-solub!e binder components cannot be used to replace Cu 2 0 and/or ZnO in a significant degree because it would increase the hydrophiiicity of the paint too much, leading to high water absorption and su bsequent early dissolution of biocides, and other soluble material throughout the film , it is Important in antifou ling paints that only the outermost layers of the paint react with seawater while the rest of the paint remains largely unreacted .
  • a second reason, explained above, is the need for a certain degree of solid soluble material so as to give rise to a porous layer with enough surface area to degrade/dissolve the relatively slow degrading/dissolving (not too hydrophiiic) binder components.
  • the present Invention provides novel self-polishing antifouling paint composition based on a new principle in that the present inventors have found that the need for seawater-soiuble pigments such as Cu 2 0 and ZnO can be
  • the invention provides novel se!f-poilshlng antifouling paint compositions comprising : 30-80 % by solids volume of the paint composition of a binder phase; 20-70 % by solids volume of the paint composition of a pigment phase, said pigment phase including solid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix; and optionally one or more solvents.
  • the invention further provides a method for the preparation of the self-polishing antifouiing paint composition as defined herein, said method comprising the step of bringing soiid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix in admixture with a binder system and one or more constituents selected from dyes, additives, solvents, pigments, fillers, fibres and anti-fou!ing agents, and any other suitable constituents to be included in either the binder phase or the pigment phase of paint compositions.
  • the invention still further provides a method for providing a self-polishing effect of a paint composition, the method comprising the step of incorporating into the paint composition soiid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix.
  • Figure 1 shows the mechanisms involved in polishing of an antifou iing coating, dividing the process into three steps.
  • An antifouiing coating consisting of a binder phase including a binder system and a discontinuous phase including pigments and/or fillers as well as the soiid particles defined herein.
  • a freshly immersed antifouiing coating will leach seawater-soiu bie pigments and the rosin constituents of the soiid particles into the sea .
  • 2 Seawater-fi!led pores left behind by the eiuted seawater-so!ub!e pigments and rosin constitute the leached layer of the coating .
  • the surface area of the water/coating interface is increased by formation of the leached layer, which allows for more interactions between water and the residues of the binder phase.
  • 3 As a result the outermost layer of the coating is released into seawater.
  • the present invention is based on the concept of including in a self-polishing antifouiing paint composition one or more rosin constituents which are entrapped or encapsulated in or within a matrix.
  • the rosin constituent in the entrapped or encapsu lated form
  • the one or more rosin constituents When preparing the paint composition, the one or more rosin constituents will essentially remain entrapped or encapsulated in the material . However, upon exposure to seawater, the rosin constituent will gradually be dissolved (possibly after hydrolysis) in the seawater which will u ltimately contribute to the seif-polisbing properties of the paint composition.
  • the present invention provides novel self-polishing antifouiing paint compositions comprising :
  • the solid particles typicaiiy have an (weight) average diameter of 0.10-50 ⁇ .
  • the paint composition (occasionally referred to as “a paint” or “a coating composition”) typicaiiy consists of a binder phase (which forms the paint film upon drying and thereby corresponds to the continuous phase of the final paint coat) and a pigments phase
  • the binder phase is in the form of a binder system .
  • Binder systems to be utilized in the present context are conventional systems as will be appreciated by the skilled person. Examples of currently preferred binder systems to be utilised within the concept of the present invention are described further below.
  • the paint composition also comprises, as a part of the pigment phase solid particles as further defined herein.
  • the binder phase constitutes 30-80 % by solids volume of the paint composition and the pigment phase constitutes 20-70 % by solids volume of the paint composition. In preferred embodiments, the binder phase constitutes 50-70 % by solids volume, such as 55-65 % by solids volume of the paint composition and the pigment phase constitutes 30-65 % by solids volume, such as 35-55 % by solids volume of the paint composition.
  • the binder phase When expressed by wet weight, typicaiiy the binder phase constitutes 15-70 % by wet weight of the paint composition and the pigment phase constitutes 20-80% by wet weight of the paint composition. In preferred embodiments, the binder phase constitutes 20-60 % by wet weight of the paint composition and the pigment phase constitutes 25-75 % by wet weight of the paint composition.
  • the binder phase constitutes 15-70 % by wet weight of the paint composition and the pigment phase constitutes 30-85 % by wet weight of the paint composition
  • the invention disclosed is copper free or copper-less, in these embodiments, the binder phase constitutes 30-85 % by wet weight of the paint composition and the pigment phase constitutes 15-40 % by wet weight of the paint composition.
  • the solid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix provide a unique possibility for providing a sufficient, even ( .a. with a limited lag-time before initiation of the polishing) and long-term self-polishing rate.
  • the term "self-polishing" is intended to mean that the paint coat ⁇ i. e. the dried/cured film of the paint composition) shou ld have a polishing rate of at least 1 ⁇ per 10,000 Nautical miles (18,520 km), determined in accordance with the "Polishing rate test" specified in the Examples section.
  • the polishing rate is in the range of 1-50 ⁇ , in particular in the range of 1-30 jm, per 10,000 Nautical miles (18,520 km) .
  • the pigment phase A main feature of the paint composition of the present invention is the inclusion of solid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix. Such solid particles constitute a part of the pigment phase of the paint composition.
  • the solid particles are meant to substitute at least a portion of seawater-soluble pigments ⁇ e.g. CujO and ZnO) frequently used in conventional self-polishing antifou iing paint composition.
  • the solid particles shou ld therefore have a suitable size in order to effectively simu late the presence of such seawater-soluble pigments.
  • the weight average diameter of the solid particles is 0.10-50 Mm, such as 0.30-40 ⁇ , or 0.50-30 Mm, or 0.80-20 ⁇ , or even 1-15 ⁇ .
  • the weight average diameter of the solid particles may be determined as described in the Examples section.
  • the expression "solid particles” is intended to mean that the particles are in solid form (i.e. non-confluent) at a temperature of 25 °C, 1 atm., at a relative humidity of 60 % for 72 hours.
  • solids particles according to the present invention are characterised by appearing in the paint composition in the same manner as conventional pigments and fillers. The solid particle defined herein will therefore appear in the final coating in the same form as the form in which they are added to the paint composition.
  • the solid particles are further characterized by consisting of one or more rosin constituents entrapped or encapsu lated in a matrix.
  • the one or more rosin constituents are typically selected from rosin (as such), rosin derivatives as well as rosin-modlfled polymers.
  • rosin is Intended to mean gum rosin; wood rosin of grades B, C, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, W-W (as defined by the ASTM D509 standard) ; virgin rosin; hard rosin; yellow dip rosin; NF wood rosin; tail oil rosin; or colophony or colophoniu m; as well as any of the single constituents of natural rosin qualities, e.g., abietic acid, abietlnic acid, sy!vic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabletic acid, neoabietic acid, pimaric acid, laevopimaric acid, isopimaric acid,
  • rosin derivative is Intended to mean ail types of rosin (as defined above) modified or derivatlsed according to any of the following chemical reactions or processes: polymerisation/oligomerisation; esterification; metal salt formation/formation of metallic resinates; ammonium salt formation; hydrogenation; dehydrogenatlon- hydrogenation/disproportionation/dismutation; as well as mixtures thereof.
  • Rosin-modified polymers are preferably those based on a polymer backbone having carboxylic acid side-chains like poly acrylates, po!ymetbacrylates and poiy(acrylate-co- methacrylate)s. Such polymers are modified with rosin or rosin derivatives via hydro!ysab!e chemical bonds, in particular ester bonds. An illustrative example is provided in the Examples section. In addition, to polymers having carboxylic acid side-chains, rosin may be modified onto polymers having hydroxyl-functiona l side groups.
  • rosin or rosin derivatives constitute at least 50 % by weight of the rosin-modified polymer.
  • the one or more rosin constituents include rosin-modified polymers, in such instances, the weight average molecular weight of the rosin-modified polymer is typically at least 1,500 g/moi, such as 1,500-200,000 g/moi, e.g. 3,000-100,000 g/moi.
  • Suitable matrices for entrapping or encapsulating the one or more rosin constituents are silica gels (e.g. silica aerogels, silica xerogeis, silica cryogels or aeromosiis), gels of carbon (e.g.
  • polyacrylamide poiy(ethyiene-co-vinyi acetate), poiy(ethyiene glycol), poly(methacryiic acid), po!y(urethanes), poiy(siioxanes), po!y(methy! methacryiate), poiy(vinyi alcohol), and poly(ethylene), poiyurethane, poiyurea, hydroiyzed poly(vinyl alcohol), phenolic resin (e.g.
  • meiamine-formaidehyde gelatin-gum arabic.
  • the stability of the matrix towards solvent should be limited to organic solvent, in seawater, the matrix should be either degradab!e, erodibie or allow for water penetration.
  • the matrix may be degraded chemically as it happens with hydrolysis in water.
  • the matrix may be eroded away by purely mechanical effects as it is occurring when solid particles are present at a surface where friction wear down the particles, or the matrix may erode away due to a collapse of the matrix after dissolution/degradation of some or ail of the entrapped rosin constituents. It is beneficial that the solid particles have low or even no solubility in conventional solvent systems used for industrial paint compositions.
  • the solid particles are mainly insoluble in xylene, typically such that at least 60 % of the weight of a sample of the solid particles is maintained after testing in the Xylene Stability Test described In the Examples section.
  • at least 70 % of the weight of a sample such as 80 % of the weight of a sample, In particular at least 85 % by weight of a sample, e.g. at least 90 % by weight of a sample, or at least 95 % by weight of a sample, Is maintained after testing in the Xylene stability Test described herein.
  • the one or more rosin constituents are entrapped in the pores of the matrix, such as a silica gel, in particular an aerogel .
  • the particles consist of rosin, a rosin derivative and/or a rosin- modified polymer entrapped in the pores of a silica gel, in particu lar an aerogel .
  • the matrix is a silica gel .
  • the matrix is a n aerogel, e.g. an aerogel of silica .
  • the material is an aerogel, e.g. an aerogel of silica where the degradation is controlled by incorporation of metal alkoxldes, optionally alkoxides wherein one or two alkoxy groups have been replaced by aikyi (e.g. Cl-6 alkyl) or aryl (e.g. phenyl) .
  • the one or more rosin constituents are encapsulated within a shell of the matrix material.
  • the shell of the matrix within which the one or more rosin constituents are encapsu lated is water-permeable.
  • the degradation of the encapsulating material happens with hydrolysis in seawater.
  • the solid particles describe hereinabove are typically present in a total amount of 1-50 % by solids volume, such as 1-30 % by solids volume, of the paint composition, e.g. 1-15 % by solids volume, or 10-30 % by solids volume.
  • the solid particles are present in an amount of 1-90 % by solids volume, such as 1-60 % by solids volume, of the pigment phase, e.g. 1-30 % by solids volume, or 20-50 % by solids volume.
  • the solid particles When expressed by wet weight, the solid particles are typically present in an amount of 1-30 % by wet weight, such as 1-20 % by wet weight, of the paint composition, e.g. 1-15 % by wet weight, or 10-30 % by wet weight.
  • the solid particles are present in an amount of 1-80 % by wet weight, such as 1-50 % by wet weight, of the pigment phase, e.g. 1-25 % by wet weight, or 15-40 % by wet weight.
  • the pigment phase e.g. 1-25 % by wet weight, or 15-40 % by wet weight.
  • the pigment phase ⁇ i.e. the phase corresponding to the discontinuous phase of the final (dry) paint coat) may in addition to the soiid particles described above also include pigments, filler, fibres and antifouling agents.
  • Such other constituents of the pigment phase ⁇ i.e. constituents besides the solid particles defined above) are not strictly mandatory components. However, such other constituents are typically Incorporated In a total amount of up to 60 %, such as up to 50 % by solids volume, e.g. in amounts of 20-50 % or 35-50 % by solids volume of the paint composition.
  • such other constituents are typically incorporated in a total amount of up to 60 %, such as up to 50 % by wet weight, e.g. in amounts of 0.1-40 %, or 0.1-30 %, by wet weight of the paint composition.
  • pigments are grades of metal oxides such as cuprous oxide (Cu 2 0) and cupric oxide (CuO) (even though e.g. cuprous oxide and cupric oxide may have antifou ling agent characteristics, it is understood that in the present context such metal oxides are only considered as "pigments"), titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red moiybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium a luminium suifosilicates, qulnacridones, phthalocyanlne blue, phthalocyanine green, titaniumdloxide, black iron oxide, graphite, indanthrone blue, cobalt aluminium oxide, carbazoie dioxazine, chromium oxide, isolndoline orange, bls-acetoacet-o-tolidioie, benz- imidazoion, quinaphta!one yellow, isolndoline yellow,
  • the Cu 2 0 content is preferably 1-40 % by solids volume, such as in the range of 5-35 % by solids volume of the paint
  • the Cu 2 0 content is preferably at least 5 % by wet weight, such as In the range of 10-75 % by wet weight of the paint composition.
  • the pigments phase may further include pigment-like ingredients such as fillers.
  • fillers are calcium carbonate, dolomite, talc, mica, barium sulfate, kaolin, silica (including pyrogenic silica, colloidal silica, fumed silica, etc.), perlite, magnesium oxide, ca icite and quartz flou r, molecu lar sieves, synthetic zeolites, calcium silicophosphate, hydrated aluminium silicate (bentonite), organo-midified clays, anhydrous gypsum, etc. These materials are characterised in that they do not render the final paint coat non- translucent and therefore do not contribute significantly to hide any material below the final paint coat.
  • fillers and pigments
  • may provide certain advantageous properties of the types provided by the additives of the binder phase e.g. as stabilizers against moisture, dehydrating agents, water scavengers, thickeners and anti-settling agents, etc.
  • particulate materials are to be construed as being part of the pigment phase.
  • fibres are e.g. those generally and specifically described in WO 00/77102, which is hereby incorporated by reference.
  • the ratio between the greatest dimension and the smallest dimension perpendicular to the length dimension in substantially ail points along the longitudinal axis (the length dimension - longest dimension) shou ld not exceed 2.5 : 1, preferably not exceeding 2 : 1.
  • the ratio between the longest dimension and the average of the two shortest dimensions should be at least 5 : 1.
  • fibres are characterised of having one long dimension and two short dimension, where the long dimension is substantially longer than the two short dimensions (typically by an order of magnitude, or even more), and the two short dimensions are substantially equal (of the same order of magnitude) .
  • the long dimension is substantially longer than the two short dimensions (typically by an order of magnitude, or even more)
  • the two short dimensions are substantially equal (of the same order of magnitude) .
  • the ratio between the two smallest dimensions of the box should be at the most 2.5 : 1 (preferably 2 : 1) and the ratio between the longest dimension of the box and the average of the to smallest dimensions of the box should be at least 5 : 1.
  • mineral fibres such as mineral-glass fibres, woilastonlte fibres, montmor!l!onite fibres, tobermorite fibres, atapuigite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool.
  • concentration of the fibres Is norma!ly In the range of 0.5-15 %, e.g. 1- 10 % by solids volume of the paint composition.
  • the concentration of the fibres is normally in the range of 0.1-20 %, e.g. 0.5-10 %, by wet weight of the paint composition.
  • the paint composition may also comprise one or more antifoulinq agents as is customary within the field.
  • antifouiing agents are: metallo-dithiocarbamates such as bis(dimethy!dithiocarbamato)zinc, ethylene-bis(dithiocarbamato)zinc, ethylene-bis(dithio- carbamato ⁇ manganese, and complexes between these; bis(l-hydroxy-2(l H)-pyridine- thionato-0,S)-copper (Copper Omadine) ; copper acryiate; bis(l-hydroxy-2( lH)-pyridine- thionato-0,S)-zinc (Zinc Omadine) ; phenyl(bispyridyl)-bismuth dichloride; metal salts such as cuprous thlocyanate, basic copper carbonate, copper hydroxide, barium metaborate, and copper sulphide; heterocyclic nitrogen compounds such as 3a
  • heterocyclic sulfur compounds such as 2-(4-thlazolyl)benzimidazoie, 4,5-dlchioro-2-n-octyi- 4-isothiazoiin-3-one, 4,5-dichioro-2-octy!-3(2H)-!sothiazoline, l,2-benzisothiazoiin-3-one, and 2-(thiocyanatomethyithlo)-benzothiazoie; urea derivatives such as N-( l,3- bis(hydroxymethyi)-2, 5-dioxo-4-imidazo!idinyi)-N, N'-bis(hydroxy methyl) urea, and N-(3,4- dichiorophenyl)-N, N-dimethyiurea, and ⁇ , ⁇ -dimethylchlorophenylurea ; amides or imldes of carboxyiic acids; su lfonic acids and of su ifenic acids such as
  • dehydroabiethyiamines and cocodimethyiamine substituted methane such as di(2-hydroxy- ethoxy)methane, 5,5'-dichioro-2,2'-dihydroxydiphenylmethane, and methylene- bisthiocyanate; su bstituted benzene such as 2,4,5, 6-tetrachloro-l,3-benzenedicarbonitrile, l, l-dichloro-N-((dimethylamino)-sulfonyl)-l-fluoro-N-phenylmethanesulfenamide, and 1- ((diiodomethyl)sulfonyl)-4-methyl-benzene; tetraaikyl phosphonium halogenides such as tri- n-butyltetradecyi phosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; disul
  • the antifouling agent is an agent that does not comprise tin.
  • the paint composition comprises an antifouling agent selected from the group consisting of pyridine-triphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo- 5-trif!uoromethyi pyrrole and imidazole containing compounds, such as medetomidine.
  • the total amount of the antifouling agent(s), if present, is typically in the range of up to 30 %, such as 0.05-25 %, by solids volume of the paint composition, e.g. 0.05-20 % by solids volume of the paint composition.
  • the total amount of the antifouling agent(s), if present is typically in the range of 0-40 %, such as 0.05-30 %, by wet weight of the paint composition, e.g. 0.05-20 % by wet weight of the paint composition.
  • the total amount of the antifouling agent(s), if present is normally in the range of 0-50 %, e.g. 0.05-25 %, by wet weight of the paint composition.
  • the binder phase of the paint composition forms the paint film upon drying and thereby corresponds to the continuous phase of the final (dry) paint coat.
  • Virtually ail binder systems conventionally used in self-polishing paint compositions may be used as the binder phase of the present paint composition. It is also found that with respect to the relative amounts of binder system vs. pigments/fi!lers/etc, only minor modifications (optimizations) may be necessary in order to obtain suitable polishing rates.
  • binder systems for marine purposes and yacht purposes, respectively, are provided in the following .
  • constituents within the binder system are especially interesting : (natural) rosin, rosin derivatives, disproportionated rosin, partly poiymerised rosin, hydrogenated rosin, gum rosin, disproportionated gum rosin, acrylic resins, polyvinyl methyl ether, and vinyl acetate-vinychloride-ethylene terpolymers.
  • Such constituents may also be present in binder systems for marine purposes.
  • po!yoxalates, silyiated acry!ate binder systems and metal acrylate binder system represent currently very interesting variants. These binder systems will - for illustrative purposes - be describe in further detail in the following.
  • non-aqueous dispersion resin non-aqueous dispersion resin
  • NAD non-aqueous dispersion resin
  • shell component a resin obtained by stably dispersing a high- polarity, high-molecular weight resin particulate component (the “core component”) into a non-aqueous liquid medium in a low-polarity solvent using a high-molecular weight component (the “shell component”).
  • shell components such as an acrylic resin or a vinyl resin may be used.
  • a copolymer of an ethylenically unsaturated monomer having a high polarity is generally applicable.
  • the core component of the non-aqueous dispersion-type resin has free acid groups or silyl ester groups that are convertible into the acid group by hydrolysis in sea water or combinations thereoff.
  • Preferably 5-75% by weight, e.g. 5-60% by weight or 7-50% by weight, of the monomers of the core polymer should carry free acid groups or silyl ester groups or combinations thereof.
  • the free acid groups will have direct influence on the properties of the paint formulation, whereas the silyl ester groups will only have influence after hydrolysis in seawater, it is presently preferred to have an overweight of free acid groups.
  • Examples of silyl ester monomers are silyl esters of acrylic or methacry!ic acid.
  • the dry weight ratio of the core component to the shell component in the NAD resin is not especially limited, but is normally in the range of 90/10 to 10/90, preferably 80/20 to 25/75, such as 60/40 to 25/75.
  • Polyoxalate binder systems are not especially limited, but is normally in the range of 90/10 to 10/90, preferably 80/20 to 25/75, such as 60/40 to 25/75.
  • binders Another interesting class of binders is the one based on polyoxalates, e.g. those disclosed in WO 2009/100908.
  • the polyoxalates may be linear or branched polymers, it is typically a copolymer, e.g. a random copolymer or block copolymer.
  • the repeating units of the polyoxalate can be saturated and/or unsaturated aliphatic and/or cycloaliphatic units and/or aromatic units. The repeating units can be unsubstituted or substituted .
  • the polyoxalate comprises at least two oxalate units, preferably at least 5 oxa late units, e.g. at least 8 oxalate units.
  • the polyoxalate will preferably be formed from the polymerisation of at least one oxalate monomer and at least one diol monomer.
  • the polyoxalates can be prepared by condensation polymerisation using any of various methods known and used in the art. Examples of common poiycondensation reactions include direct esterification reaction between oxalic acid and dlois; transesterification reaction between dia lkyi oxalates and diois; reaction in solution between oxalyl chloride with diols; and interfacla! condensation reaction between oxalyl chloride and diols or alkali salts of diols or between alkali salts of oxalic acid, such as sodium oxalate or potassium oxalate, and diols.
  • the poiycondensation reactions can be carried out as melt or in solution.
  • the polymerisation can be performed under melt poiycondensation condition or in solution.
  • the oxalate monomer used in the polymerisation reaction may be an ester of oxalic acid, especia lly a diester.
  • Esters may be alkyl esters, aikenyl esters or aryl esters.
  • suitable dia!kyl oxalates for the preparation of polyoxalates include dimethyl oxalate, diethyl oxalate, dipropyl oxa late and dibutyl oxalate.
  • Dialkyi oxalates are preferred .
  • diols for the preparation of polyoxalates Include saturated aliphatic and saturated
  • cycloaliphatic diols unsaturated aliphatic diols or aromatic diois.
  • Linear or branched saturated aliphatic diols are preferred.
  • the above mentioned diols can be used alone or in combination of two or more diols. Preferably a mixture of two or more diols is used to manufacture the polyoxalates.
  • Branching In polymers and "star" shaped polymers are examples of useful structural variables that can be used advantageously to modify polymer properties such as solubility in organic solvents, miscibility in polymer blends and mechanical properties.
  • siiyiated acryiate is intended to cover siiyiated acryiate co-polymers having at least one side chain bearing at least one terminal group of the general formula i :
  • n Is 0 or an integer of 1 or more and X, R lf R 2 , R 3 , R 4 and R 5 are as defined above.
  • Ri-R 5 are each groups selected from the group consisting of C 1-20 -alkyl, C 1-20 -alkoxy, phenyl, optionally substituted phenyl, phenoxy and optionally substituted phenoxy. With respect to the above formula I it is generally preferred that each of the a lkyl and alkoxy groups has up to about 5 carbon atoms (C 1-5 -alkyi) . illustrative examples of substituents for the substituted phenyl and phenoxy groups include halogen, C 1-5 -alkyl, C 1-5 -alkoxy or C 1-10 -alkylcarbonyl . As indicated above, R-, -R 5 may be the same or different groups.
  • the co-polymers preferably have weight average molecular weights in the range of 1,000- 1,500,000, such as in the range of 5,000- 1,500,000, e.g. in the range of 5,000-1,000,000, in the range of 5,000-500,000, in the range of 5,000-250,000, or in the range of 5,000- 100,000.
  • R 3 , R 4 and R 5 may be the same or different, such as Ci. 20 -alkyl (e.g. methyl, ethyl, propyl, butyl, cycloalkyl such as cyclohexyl and substituted cyclohexyi) ; aryl (e.g. , phenyl and naphthyl) or substituted aryl (e.g. , substituted phenyl and substituted naphthyl) .
  • substituents for aryl are halogen, C 1-18 -alkyl, C 1-10 -acyl, sulphonyl, nitro, and amino.
  • Suitable methacryiic acid-derived monomers bearing at least one terminal grou p of the general formula ⁇ include trimethylsilyl (meth)acryiate, triethyl- si!yi(metb)acry!ate, tri-n-propylsilyl(meth)acrylate, triisopropylsi!yl (meth)acrylate, tri-n- butvisilyl (meth)acry!ate, triisobutyisilyl (metb)acry!ate, tri-tert-butyisi!y!(meth)acryiate, tri- n-amylsilyl (meth)acry!ate, tri-n-bexyisi!y!
  • the si!ylated acryiate may comprise monomer units with a terminal group of the genera! formula ⁇ (as discussed above) in combination with a second monomer B of the genera! formula II :
  • monomer B which has a (meth)acry!oy!oxy group in a molecu le examples include methoxyethy! (meth)acry!ate, ethoxyethy! (meth)acry!ate, propoxyethy! (meth)acry!ate, butoxyethy! (meth)acry!ate, hexoxyethy! (meth)acry!ate, methoxydiethy!ene glycol
  • the si!ylated acryiate may comprise a co-polymer having monomer units with a terminal group of the genera! formula I (as discussed above) in combination with a second monomer C of the genera! formula III : F3 ⁇ 4
  • Y is an acry!oy!oxy group, a methacry!oy!oxy group, a maieinoyloxy group or a fumaroy!oxy group, and both of R s and R 7 are CV ⁇ -aiky! .
  • R s and R 7 are CV ⁇ -aiky! .
  • silyl ester-type binders are the low molecular weight variants disclosed in WO 2005/005516.
  • the binder is a si!y! ester copolymer is a copolymer comprising at least one side chain bearing at least one terminal grou p of the formula :
  • n is 0 or an integer of 1 to 50
  • Rl, R2, R3, R4, and R5 are each independently selected from the group consisting of optionally substituted Ci. 2 o-alkyl, optionally substituted Ci-2o-alkoxy, optionally substituted ary!, and optionally substituted aryioxy, and having a weight-average molecu lar weight less of than 20,000, a polydispersity of less than 3.0, a glass tra nsition temperature below 90 °C, with less than 70 weight per cent of said silyl ester copolymer consisting of side chains having a silyl ester functionality. See in WO 2005/005516 for further details about such binder components.
  • metal acrylate is intended to cover co-polymers having at least one side chain bearing at least one terminal group of the general formula IV
  • M is a metal having a valency of 2 or more; n is an integer of 1 or more with the proviso that n+ l equals the metal valency; L is an organic acid residue and each L is independently selected from the group consisting of wherein R 4 is a monovalent organic residue, or L is -OH or combinations thereof; R 3 is hydrogen or a hydrocarbon group having from 1 to 10 carbon atoms.
  • Examples of monomers having a terminal group of the general formulae IV are acid-functional vinyl poiymerisable monomers, such as methacryiic acid, acrylic acid, p- styrene sulfonic acid, 2-methyi-2-acrylamide propane su lfonic acid, methacryl acid phosp oxy propyl, methacryl 3-chloro-2-acid phosphoxy propyl, methacryl acid phosphoxy ethyl, itaconic acid, maieic acid, maleic anhydride, monoalky! itaconate (e.g.
  • acid-functional vinyl poiymerisable monomers such as methacryiic acid, acrylic acid, p- styrene sulfonic acid, 2-methyi-2-acrylamide propane su lfonic acid, methacryl acid phosp oxy propyl, methacryl 3-chloro-2-acid phosphoxy propyl, methacryl acid phosphox
  • methyl, ethyl, butyl, 2-ethyl hexyl monalkyi ma!eate
  • monalkyi ma!eate e.g. methyl, ethyl, butyl, 2-ethyl hexyl ; half-ester of acid anhydride with hydroxy! containing poiymerisable unsaturated monomer (e.g. half-ester of succinic anhydride, maieic anhydride or phthalic anhydride with 2-hydroxy ethyl methacry!ate.
  • the above-mentioned monomers may be co-po!ymerised (in order to obtain the co-polymer with one or more vinyl poiymerisable monomers.
  • vinyl poiymerisable monomers are methyl acryiate, methyl methacryiate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyi methacrylate, 2-ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, methoxy ethyl
  • any metal having a valency of 2 or more may be used.
  • suitable metals include Ca, I g, Zn, Cu, Ba, Te, Pb, Fe, Co, Ni, Bi, Si, Ti, M n, Al and Sn.
  • Preferred examples are Co, Ni, Cu, Zn, M n, and Te, In particular Cu and Zn.
  • the metal When synthesising the metal-containing co-polymer, the metal may be employed in the form of its oxide, hydroxide or chloride.
  • the metal acryiate co-polymer may be prepared as described in e.g. EP 0 471 204 Bl, EP 0 342 276 Bl or EP 0 204 456 Bl .
  • the organic acid side groups need to contain a meta! ester bond ; some of the organic acid side grou ps may be left un-reacted in the form of free acid, if desired .
  • the weight average molecular weight of the metal-containing co-polymer is generally in the range of from 1,000 to 150,000, such as in the range of from 3,000 to 100,000, preferably in the range of from 5,000 to 60,000.
  • binder systems may include therein - as a part of the binder system - one or more further binder components, it should be understood that the binder components mentioned below may aiso constituted the binder system, cf. the general presentation of the binder system .
  • rosin and rosin derivatives are : rosin and rosin derivatives (see definition further above) Including metal salts of rosin, oils such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soy bean oil and derivatives thereof; and other polymeric binder components such as saturated polyester resins; polyvinylacetate, polyvlnylbutyrate, po!yvinylchloride-acetate, copolymers of vinyl acetate and vinyl isobutyl ether; vinylchloride; copolymers of vinyl chloride and vinyl Isobutyl ether; aikyd resins or modified aikyd resins; hydrocarbon resins such as petroleum fraction condensates; chlorinated polyoiefines such as chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene; styrene copolymers such as styrene/butadiene copolymers, styrene/methacryi
  • polyurethanes such as those genera lly and specifically defined In WO 97/44401 that is hereby incorporated by reference.
  • Such further binder components typically constitutes 0-10 % by solids volu me of the paint composition.
  • the dry matter of such further binder components is typically 0-10 % by wet weight of the paint composition.
  • the binder phase ⁇ i.e. the phase corresponding to the continuous phase of the final (dry) paint coat
  • the binder system including the further binder components
  • the binder phase of paint compositions may - besides the binder system (including the further binder components) - of course also Include dyes, additives and solvents, as well as other suitable constituents to be included in the binder phase of paint compositions.
  • dyes examples include l,4-bis(butylamino)anthraquinone and other anthraquinone
  • additives are plasticizers such as chlorinated paraffin; phthalates such as dibutyl phthalate, benzyibutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; phosphate esters such as tricresyl phosphate, nonylphenol phosphate, octyl- oxipoiy(ethyleneoxy)ethyl phosphate, tributoxyethyl phosphate, isooctylphosphate and 2- ethy!hexyl dipheny!
  • plasticizers such as chlorinated paraffin
  • phthalates such as dibutyl phthalate, benzyibutyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate
  • phosphate esters such as tricresyl phosphate, nonylphenol phosphate, oct
  • su lfonamides such as N-ethyl-p-toluensulfonamide, a!ky!-p- toluene sulfonamide
  • adipates such as bis(2-ethyihexyi)adipate), diisobutyl adipate and dl- octyiadipate
  • surfactants such as derivatives of propylene oxide or ethylene oxide such as a!kyipbeno!-ethy!ene oxide condensates; ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid ; sodium dodecyl sulfate; a!kylphenol ethoxylates; and soya lecithin; wetting agents and dispersants; defoaming agents such as silicone oils; stabilisers such as stabilisers against light and heat, e.g.
  • HALS hindered amine light stabilisers
  • 2-nydroxy-4-methoxybenzophenone 2-(5-chloro- (2H)-benzotriazol-2-yl)-4-methyl-6-(tert-buty I) phenol, and 2,4-ditert-buty!-6-(5- cb!orobenzQtriazoi-2-yi)pbeno!
  • stabilisers against moisture or water scavengers substituted isocya nates, substituted siianes and ortho formic acid triethyi ester
  • stabilisers against oxidation such as butyiated hydroxyanisoie; butyiated hydroxytoluene; propy!gailate; toco- pherols; 2, 5-di-tert-buty!-hydroquinone; L-ascorby! pa!mltate; carotenes; vitamin A;
  • inhibitors against corrosion such as aminocarboxy!ates, ammonium benzoate, barium/- ca icium/zinc/magnesium salts of aikylnaphthalene sulfonic acids, zinc phosphate; zinc metaborate; coalescing agents such as glycols, 2-butoxy ethanoi, and 2,2,4-trimethyi-l,3- pentanediol monoisobutyrate; and thickeners and anti-settling agents such as
  • Dehydrating agents such as orthopropionic acid ester, orthoformic acid ester, orthoacetic acid ester, aikoxysilane, aikyi silicates like tetra ethyl ortosilicate, or isocyanates.
  • the paint compositions comprise dyes and additives in a cumulative amount of 0-20 %, e.g. 1-20 %, by solids volume of the paint composition.
  • the paint compositions comprise dyes and additives in a cu mulative amount of 0-10 %, e.g. 1-10 %, by wet weight of the paint composition.
  • solvents examples include alcohols such as methanol, ethanoi, propanoi, isopropanol, butanol, isobutanoi and benzyl alcohol ; aliphatic, cycloaiiphatic and aromatic hydrocarbons such as white spirit, cyciohexane, toiuene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cycio- hexanone; ether alcohols such as 2-butoxyethanol, propylene glycol monomethyl ether, ethylene glycol monoethyi ether, ethyl ether and butyl dlglycoi; esters such as ethyl acetate, propyl acetate, methoxypropyi acetate, n-buty! acetate and 2-ethoxye
  • chlorinated hydrocarbons such as methylene chloride, tetrachioroethane and
  • the paint compositions comprise one or more solvents in a cumulative amount of 0-60 %, e.g. 10-60 %, by wet weight of the paint composition.
  • % by wet weight is Intended to mean the weight/weight percentage of the wet matter of the paint composition. It should be understood that solvents are Included.
  • volume/volume percentage of the solid ⁇ i.e. non-volatile matter of the paint composition It should be understood that any solvents ⁇ i.e. volatiles) are disregarded.
  • the solid particles may be prepared by encapsulation methods such as micro encapsulation, where the end result is small particle composed of one material (core/internal phase/fill) confined within one or more uniform wali(s) of a different material(s) (shell/membrane) .
  • Micro capsu les can be prepared by physical methods such as pan coating, air-suspension coating, centrifugal extrusion, spray-drying, and the use of vibrational nozzle techniques to prepare core-shell encapsulation or microgranu iation. Or they can be prepared by physico- chemical methods such as ionotropic gelation, coacervation. Also, chemical methods can be applied; these are interfacla! polycondensation, interfacia! cross-linking, in-situ
  • the solid particles may be prepared by entrapment of the one or more rosin constituents in a matrix that allows for contact between the entrapped materia! and the surroundings, but effectively hinders diffusion or dissolution of the entrapped materia! in the solvent.
  • Solid particles based on entrapment may be prepared by polymerisation of materlai in-situ in a porous structure, such as an aerogel, a xeroge!, a cryogel or an aeromosii.
  • the solid particles may also be prepared by introducing the one or more rosin constituents into a porous structure by immersing a suitable porous material in a melt or solution of the one or more rosin constituents. Diffusion and capillary forces will then drive the one or more rosin constituents into the pores of the porous material.
  • silica aerogel is typically done by the sol-gel process. First a gei Is created In solution and then the liquid is carefully removed to leave the aerogel intact. The first step is the creation of a colloidal suspension of solid particles known as a "sol".
  • Silica aerogel is made by the creation of colloidal silica. The process starts with a liquid alcohol like ethanoi which is mixed with a silicon alkoxide precursor, for example tetramethyi orthosiiicate (TMOS) or tetraethyl orthosiiicate (TEOS). A hydrolysis reaction forms particles of silicon dioxide forming a so! solution. The oxide suspension begins to undergo condensation reactions which resuit in the creation of metal oxide bridges (either M-O-M, "oxo" bridges or M-OH-M, "ol” bridges) linking the dispersed colloidal particles.
  • metal oxide bridges either M-O-M, "oxo" bridges or M-OH-M, "ol” bridges
  • the present invention provides a seif-po!ishlng antifouilng paint composition comprising: 50-75% by solids volume of the composition of a binder system,
  • pigment phase comprising solid particles consisting of a rosin-modified polymer entrapped in a matrix In an amount of 1-49% by solids volume, and a metailo-organic or organic antifouiing agent in an amount of 0.05-20% by solids volume;
  • the present invention provides a self-polishing antifouiing paint composition comprising :
  • pigment phase comprising solid particles consisting of rosin or rosin derivatives encapsu lated in a matrix in an amount of 1-49% by solids volume, and an inorganic, metailo-organic or organic antifouiing agent in an amount of 0.05-20% by solids volume;
  • the present invention provides a self-polishing antifouiing paint composition comprising :
  • said pigment phase comprising solid particles consisting of rosin or rosin derivatives entrapped in a silica aerogel matrix in an amount of 1-49% by solids volume, and a metailo- organic or organic antifouiing agent in an amount of 0.05-20% by solids volume; and optionally one or more solvents.
  • the present invention also provides a method for the preparation of the self-polishing antifouiing paint composition as defined herein, said method comprising the step of bringing solid particles consisting of one or more rosin constituents entrapped or encapsu lated in a matrix in admixture with a binder system and one or more constituents selected from dyes, additives, solvents, pigments, fillers, fibres and antl-fouling agents, and any other suitable constituents to be included in either the binder phase or the pigment phase of paint compositions.
  • the paint composition of the present invention is prepared usually by mixing and dispersing the above components all at once or in a divided fashion by a conventional apparatus for producing paint composition (paints), such as a ball mill, a pearl mill, a three-roll mill, a high speed disperser.
  • paint compositions according to the invention may be filtrated using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration.
  • the paint composition of the present invention thus prepared may be coated as it is or after having the viscosity adjusted by a diluting solvent, on a ship or a maritime structure having a rust preventive coating material coated thereon, by e.g. airless spray-coating, air spray-coating, roller coating or brush coating.
  • a rust preventive coating material coated thereon by e.g. airless spray-coating, air spray-coating, roller coating or brush coating.
  • the exact technique chosen depends upon the object to be protected and also upon the particular composition (such as its viscosity etc.) and upon the particular situation.
  • Preferred applications techniques are spraying and by means of a brush or a roller.
  • the solid particles consisting of one or more rosin constituents entrapped or encapsulated in a matrix are added to the paint composition as powders.
  • the paint composition comprises solvent(s) so that the solids volume ratio (SVR) is in the range of 30- 100 %, such as 30-70 %.
  • SVR solids volume ratio
  • the invention further relates to a marine structure coated with one or several layers, in particular successive layers, of a paint composition as defined hereinabove.
  • the paint composition according to the invention may be applied to a marine structure to be protected in one or several successive layers, typically 1 to 5 layers, preferably 1 to 3 layers.
  • the dry film thickness (DFT) of the coating applied per layer will typically be 10 to 300 Mm, preferably 20 to 250 Mm, such as 40 to 200 jm.
  • the total dry film thickness of the coating will typically be 10 to 900 ⁇ , preferably 20 to 750 ⁇ , in particu lar 40 to 600 ⁇ , such as 80 to 400 ⁇ .
  • the marine structure to which the paint composition according to the invention may be applied to may be any of a wide variety of solid objects that come into contact with water, for example vessels (Including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines (both nuclear and conventional), and naval vessels of ail types) ; pipes; shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, floatation devices, underwater oil well structures etc; nets and other maricuiture
  • vessels including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines (both nuclear and conventional), and naval vessels of ail types
  • pipes shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, floatation devices, underwater oil well structures etc; nets and other maricuiture
  • the marine structure may first be coated with a primer-system which may comprise several layers and may be any of the conventional primer systems used In connection with application of paint compositions to marine structures.
  • the primer system may include an anti-corrosive primer optionally followed by a layer of an adhesion-promoting primer.
  • the above-mentioned primer system may, for example, be a combination of an epoxy resin having an epoxy equivalent of from 160 to 600 with its curing agent (such as an amino type, a carboxyilc acid type or an acid anhydride type), a combination of a poiyoi resin with a polyisocyanate type curing agent, or a coating material containing a vinyl ester resin, an unsaturated polyester resin or the like, as a binder system, and, if required, further containing a thermoplastic resin (such as chlorinated rubber, an acrylic resin or a vinyl chloride resin), a curing accelerator, a rust preventive pigment, a colouring pigment, an extender pigment, a solvent, a triaikoxysilane compound, a piasticizer, an additive (such as an antisagging agent or a precipitation preventive agent), or a tar epoxy resin type coating material, as a typical example.
  • a thermoplastic resin such as chlorinated rubber, an acrylic resin or a vinyl chloride
  • the present invention further provides the use of solid particles consisting of one or more rosin constituents entrapped or encapsulated in a matrix in a paint composition to provide self-polishing properties to said paint composition.
  • the present invention further provides a method for providing a self-polishing effect of a paint composition, the method comprising the step of incorporating into the paint composition solid particles consisting of one or more rosin constituents entrapped or encapsulated in a matrix.
  • paint compositions defined herein may comprise one, two or more types of the individual constituents, in such embodiments, the total amount of the respective constituent should correspond to the amount defined above for the individual constituent.
  • the "(s)” in the expressions: pigment(s), fil!ers(s), agent(s), etc. indicates that one, two or more types of the individual constituents may be present.
  • the average particle size and the particle size distribution of the solid particles can be established using a Maivern Mastersizer 2000 from Malvern instruments, and a Hydro 2000G sample disperser. Measurements may be done on a suspension of the solid particles in organic solvents such as ethanol or xylene.
  • Polishing and leaching characteristics are measured using a rotary set-up similar to the one described by Kiii et ai.
  • the set-up consists of a rotary rig, which has two concentric cylinders with the inner cylinder (rotor, diameter of 0.3 m and height 0.17 m) capable of rotation.
  • the cylinder pair is immersed in a tank containing about 400-500 litres of Artificial Seawater (cf. Table 1) .
  • the tank is fitted with baffles to break the liquid flow, which enhances turbulence and enables faster mixing of the species released from the paints and enhance heat transfer from a thermostating system .
  • the purpose of using two cylinders is to create a close approximation to couette flow (flow between two parallel wails, where one wall moves at a constant velocity) .
  • the rotor is operated at 20 knots at 25 °C (unless otherwise specified), and the pH is adjusted frequently to 8.2 using 1 M sodium hydroxide or 1 M hydrochloric acid .
  • Samples are prepared using overhead transparencies (3M PP2410) that are primed using two-component paint (Hempadur 45182 ex Hempei A/S) applied using a Doctor Blade applicator with a gap size of 200 ⁇ . Coating samples are appiied adjacent to each other using a Doctor Blade applicator with a gap of 500 ⁇ . After drying for 1 day, the coated transparency is cut in strips of 2 cm resulting in eight samples of 1.5 x 2 cm 2 on a long (21 cm) strip. The strips are mounted on the rotor, and left to dry for a week.
  • 3M PP2410 that are primed using two-component paint (Hempadur 45182 ex Hempei A/S) applied using a Doctor Blade applicator with a gap size of 200 ⁇ . Coating samples are appiied adjacent to each other using a Doctor Blade applicator with a gap of 500 ⁇ . After drying for 1 day, the coated transparency is cut in strips of 2 cm resulting in eight samples of 1.5
  • An acrylic test panel (15 x 20 cm 2 ), sandblasted on one side to facilitate adhesion of the coating, is first coated with 80 um (DFT) of Hempatex high-build 4633 from Hempei A/S (a system based on chlorinated rubber binders) applied by air spraying .
  • DFT Hempatex high-build 4633 from Hempei A/S (a system based on chlorinated rubber binders) applied by air spraying .
  • the test paint After a minimum drying time of 24 hours in the laboratory at room temperature the test paint is applied with a Doctor Blade type applicator, with four gap sizes with a film width of 80 mm .
  • One coat was appiied in a DFT of 90-100 ⁇ . After at least 72 hours drying the test panels are fixed on a rack and immersed in sea water.
  • the panels are immersed in seawater with salinity in the range of 29-31 parts per thousand at a temperature in the range of 29-31°C. in Spain the panels are immersed in the Mediterranean, where the temperature varies between 13 and 25 °C depending on the season.
  • the fouling species of most relevance are animals. For animal fouling a level of 1 is considered good. For algal fou ling, a level of up to grade 2 is acceptable.
  • Dissolution rate of rosin constituents from solid particles in artificial seawater The release rate of rosin from the soiid particles may be measured by exposure to artificial seawater under dynamic conditions.
  • the soiid is ground using a mortar.
  • a suspension of the ground particles is prepared in artificial seawater.
  • the suspension is placed on a stirring table at 25 °C for three weeks the suspension is centrifuged.
  • a sample of the supernatant Is taken out, and the concentration of degraded or dissolute particle material in the artificial seawater is measured .
  • Measuring the concentration of rosin in artificial seawater may be done by extracting the rosin into toluene solution containing 0.1 % of an internal standard (e.g.
  • Stability of solid particles immersed in xylene (The Xylene Stability Test) A lump of approximately 0.5 g of a sample of soiid particles is weighed and immersed in at least 5 g of xylene. The container Is kept at 25 °C. Every 48-36 hours the sample is taken out of the container, dried at 25 °C in a fume hood to constant weight, after which the sample is weighed and again put into at least 5 g of pure xylene. The procedure is repeated for at least 6 days or until a stable weight of the sample has been reached. Stability of solid particles immersed in toluene
  • the reactor is flowed with C0 2 at 100 bars pressure and a temperature of 40 °C for 9 hours at a flow rate of 6-7 g C0 2 /minut. After this, C0 2 gas is slowly vented off during several hours leaving the dry hydrophilic silica aerogel for collection from the vessel.
  • MTMS methyltrimethoxysilane
  • Example 2 Preparation of rosin-filled gel material.
  • the material produced in example 1 is crushed to produce small lumps below 1 cm 3 and placed in a container with an excess of hydrogenated rosin (Eastman Forai AX-E Fully hydrogenated rosin).
  • the container is heated to 140 °C and kept at this temperature for a time not exceeding 4 hours.
  • the filled gel is separated from the molten rosin before cooling.
  • the materia! is ground to obtain a powder.
  • the waxy yellowish material is redisso!ved in methylene chloride and washed with a 5% aqueous solution of sodium hydroxide, followed by washing with a brine solution and finally with water.
  • the methylene chloride solution is dried over sodium sulphate and the solvent is removed by vacuum distiliation.
  • Example 2 An aerogel prepared as described in Example 1 is placed In a container with a solution of the rosin-monomer and a few percent azobisisobyronitrlie (AIBN) . The solvent is allowed to evaporate, and xylene is added . The suspended material is heated to 85 °C. Polymerisation is allowed to take place for 15 minutes before the material is cooled and washed several times with xylene in order to remove unreacted rosin-monomers. The materia! is ground to obtain a powder, in one example a weight average diameter of 41 m was obtained .
  • AIBN azobisisobyronitrlie
  • Mode! paint with encapsulated rosin having the composition specified below can be prepared by adding the raw materials to a suitable container.
  • a solvent e.g . xylene or a mixture of xylene and methyl iso-buty! ketone (MIBK)
  • MIBK methyl iso-buty! ketone
  • the paint is mixed on a high speed disso!ver. Glass pearls are added to crush the pigments to a fineness of grind below 60 ⁇ .
  • the dispersion is ended when a suitable fineness of grind has been obtained, and the temperature to activate the thixotropic agents (additives) has been reached.
  • Binder system comprised of 57 57 57
  • Binder system 50 50 comprised of
  • the silica aerogel matrix is completely insoluble in xylene.

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Abstract

La présente invention concerne de nouvelles compositions de peinture antisalissure auto-polissante comprenant : 30-80 % en volume de matières solides de la composition de peinture d'une phase de liant ; 20-70 % en volume de matières solides de la composition de peinture d'une phase pigmentaire, ladite phase pigmentaire comprenant des particules solides consistant en un ou plusieurs constituants à base de colophane (par exemple colophane, dérivés de la colophane ou polymères modifiés par de la colophane) piégés ou encapsulés dans une matrice (par exemple une silice telle qu'un aérogel de silice) ; et éventuellement un ou plusieurs solvants. L'invention concerne en outre a) un procédé de préparation de la composition de peinture antisalissure auto-polissante, consistant à amener des particules solides consistant en un ou plusieurs constituants à base de colophane piégés ou encapsulés dans une matrice en mélange avec un système de liant et un ou plusieurs constituants choisis parmi les colorants, les additifs, les solvants, les pigments, les charges, les fibres, les agents antisalissure, et autres constituants appropriés devant être inclus soit dans la phase de liant soit dans la phase pigmentaire des compositions de peinture ; b) un procédé consistant à fournir un effet auto-polissant d'une composition de peinture, le procédé comprenant l'étape consistant à incorporer dans la composition de peinture les particules solides ; et c) une structure marine.
PCT/DK2012/050331 2011-09-06 2012-09-06 Composition de peinture antisalissure auto-polissante comprenant des particules solides de constituant de colophane piégés ou encapsulés WO2013034158A1 (fr)

Priority Applications (3)

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CN201280043063.4A CN103857754A (zh) 2011-09-06 2012-09-06 含捕获或包封的松香成分的固体颗粒的自抛光的防污漆组合物
EP12829513.6A EP2753665A4 (fr) 2011-09-06 2012-09-06 Composition de peinture antisalissure auto-polissante comprenant des particules solides de constituant de colophane piégés ou encapsulés
US14/342,948 US20140242403A1 (en) 2011-09-06 2012-09-06 Self-polishing antifouling paint composition comprising solid particles of entrapped or encapsulated rosin constituents

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9334196B2 (en) 2014-09-19 2016-05-10 Magneco/Metrel, Inc. Paint composition for concrete and masonry surfaces
US9512042B2 (en) 2014-09-19 2016-12-06 Magneco/Metrel, Inc. Method of coating concrete and masonry surfaces
CN106801451A (zh) * 2017-02-27 2017-06-06 苏州科斯曼照明工程有限公司 一种室外消防栓阀体内壁的养护方法
WO2017204763A1 (fr) * 2016-05-23 2017-11-30 Ataturk Universitesi Bilimsel Arastirma Projeleri Birimi Peinture à caractéristique d'isolation thermique
US9994486B1 (en) 2017-03-16 2018-06-12 Magneco/Metrel, Inc. Refractory composition resistant to high temperature shock and creep
US10233335B2 (en) 2016-08-12 2019-03-19 Magneco/Metrel, Inc. Protective coating composition for molten aluminum and alkali metal environments
US10429130B2 (en) 2017-03-16 2019-10-01 Magneco/Metrel, Inc. Refractory kiln car resistant to high temperature shock and creep
US10494305B2 (en) 2017-03-16 2019-12-03 Magneco/Metrel, Inc. Method of making refractory article resistant to high temperature shock and creep
US10590283B2 (en) 2016-08-12 2020-03-17 Magneco/Metrel, Inc. Method of providing a protective coating composition for molten aluminum and alkali metal environments

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9932486B1 (en) * 2016-10-05 2018-04-03 Eastman Chemical Company Coalescent and non-ionic surfactant blend
CN106977659A (zh) * 2017-04-28 2017-07-25 华南理工大学 一种后接枝法制备的主链降解型聚丙烯酸锌树脂及其方法与应用
CN109233532A (zh) * 2017-05-04 2019-01-18 江苏海晟涂料有限公司 一种海洋装备用高固厚膜耐蚀防污环保型涂料
KR101933797B1 (ko) * 2017-08-08 2018-12-28 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 제조된 성형품
EP3587505A1 (fr) * 2018-06-29 2020-01-01 Aerogel ApS Biocides et biorépulsifs encapsulés
WO2021130289A1 (fr) * 2019-12-27 2021-07-01 Aerogel Aps Utilisation de compositions d'aérogel biocide dans des peintures, des revêtements et des agents d'étanchéité en mer
CN116694116A (zh) * 2023-05-17 2023-09-05 江苏泛亚微透科技股份有限公司 自抛光表面防污涂料及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009062518A1 (fr) * 2007-11-12 2009-05-22 Biolocus A/S Composition antisalissure comprenant un aérogel
WO2011107521A2 (fr) * 2010-03-02 2011-09-09 Fibac Aps Particules de gel chargées pour compositions antisalissure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7226484B2 (en) * 1994-04-19 2007-06-05 Applied Elastomerics, Inc. Tear resistant gels and articles for every uses
EP1308484A1 (fr) * 2001-10-30 2003-05-07 Sigma Coatings B.V. Emploi des esters silyliques de la colophane dans des peintures auto-polissantes et antisalissures
ES2265060T3 (es) * 2001-12-20 2007-02-01 Hempel A/S Composicion de pintura antiincrustante con base de dispersion no acuosa.
EP2025364A1 (fr) * 2007-08-13 2009-02-18 Procter & Gamble International Operations SA. Compositions comprenant des particules chargées de colorant
EP2260081B1 (fr) * 2008-03-25 2014-11-26 Xerox Corporation Nanopigments organiques encapsulés dans de la silice et leurs procédés de production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009062518A1 (fr) * 2007-11-12 2009-05-22 Biolocus A/S Composition antisalissure comprenant un aérogel
WO2011107521A2 (fr) * 2010-03-02 2011-09-09 Fibac Aps Particules de gel chargées pour compositions antisalissure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2753665A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9334196B2 (en) 2014-09-19 2016-05-10 Magneco/Metrel, Inc. Paint composition for concrete and masonry surfaces
US9376575B2 (en) 2014-09-19 2016-06-28 Magneco/Metrel, Inc. Method of making paint composition for concrete and masonry surfaces
US9512042B2 (en) 2014-09-19 2016-12-06 Magneco/Metrel, Inc. Method of coating concrete and masonry surfaces
WO2017204763A1 (fr) * 2016-05-23 2017-11-30 Ataturk Universitesi Bilimsel Arastirma Projeleri Birimi Peinture à caractéristique d'isolation thermique
US10233335B2 (en) 2016-08-12 2019-03-19 Magneco/Metrel, Inc. Protective coating composition for molten aluminum and alkali metal environments
US10590283B2 (en) 2016-08-12 2020-03-17 Magneco/Metrel, Inc. Method of providing a protective coating composition for molten aluminum and alkali metal environments
CN106801451A (zh) * 2017-02-27 2017-06-06 苏州科斯曼照明工程有限公司 一种室外消防栓阀体内壁的养护方法
US9994486B1 (en) 2017-03-16 2018-06-12 Magneco/Metrel, Inc. Refractory composition resistant to high temperature shock and creep
US10429130B2 (en) 2017-03-16 2019-10-01 Magneco/Metrel, Inc. Refractory kiln car resistant to high temperature shock and creep
US10494305B2 (en) 2017-03-16 2019-12-03 Magneco/Metrel, Inc. Method of making refractory article resistant to high temperature shock and creep

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EP2753665A1 (fr) 2014-07-16
CN103857754A (zh) 2014-06-11
US20140242403A1 (en) 2014-08-28

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